Metal, phosphorus, and sulfur-containing organic compounds



METAL, PHOSPHORUS, AND SULFUR-CON- TAINING ORGANIC COMPOUNDS Joseph M. Hersh, Ponca City, Okla, aasignor to Continental Oil Company, Ponca City, Okla, a corporation of Delaware No Drawing. Original application August 9, 1945,

Serial No. 609,809. Divided and this application March 30, 1946, Serial No. 658,574

18 Claims.

1 This invention relates as indicated to lubricants but in its broader aspects includes the provision of new compositions of matter and methods of producing the same, which materials taining organic compound with a metal and sulfur containing reagent; or more specifically the material containing phosphorus, sulfur, and a metal in chemical combination produced by treathave among their many uses that of an improv- 5 ing the reaction product of an organic compound ing agent for mineral lubricating oils. and a ph phorus and sulfur containing re n This application is a division of my copendinz with a metal and s r c i i r a t. application Serial No. 609,809, filed August 9, II. The method of producing an organic mate- 1945. rial containing phosphorus, sulfur, and a metal While the present invention in its broader asin chemical c mbination which comprises treatpects thus provides new materials or composiing a phosphorus and sulfur containing organic tions of matter which will be found of utility compound with a metal and sulfur containing in other fields of use, their particular usefulness reagent; or more specifically the method of proas an improving agent for lubricating composiducing a material containing phosphorus, sultions will be referred to as illustrative of their f and a metal in chemical combination which many properties since such use is in itself a part comprises treating the reaction product of an of the present invention. It is, therefore, an o ganic compound and a phosphorus and sulfur object of this invention to provide a poly-funccontaining agent with a metal and sulfur contional additive for hydrocarbon products which taining reagent. will inhibit corrosion, sludge, acidity, and lacquer III. A lubricating composition comprising a formation on lubricated parts. mineral oil solution of a material containing phos- Another object of this invention is to pro- D r sulfur, and a metal in chemical comvide a poly-functional additive which has parbination produced by treating a phosphorus and ticular storage stability in hydrocarbon oil blends. sulfur containing organic compound with a t l A further object of this invention is to proand sulfur containing reagent; or more specifivide a poly-functional lubricant additive having cally a lubricating composition comprising a minimproved solubility characteristics in hydrocareral oil solution of a material containing phos hon oils of the lubricant type. phorus, sulfur, and a metal in chemical combina- A still further object of this invention'is to tion pr y treating the reaction Product provide a lubricant additive composition which Of a Organic compound and a phosphoru and has particular stability tohydrolysis under confur o ai g reagent with a metal and sulditions of atmospheric storage either alone or i111 containing reagentin in r l 11 blends, It will be observed from the ensuing descrip- Yet a further object of this invention is to 191011 that in its bmfidciit a p the pr s nt inprovide a poly-functional additive having parvention is concerned with organic materials conticular and outstanding thermal stability in hyning phosp o us, Sulfur, and a metal in chemdrocarbon oil blends. ical combination, which material has preferen- An additional bject of t invention is t tially a substantial amount of titratable alkaprovide a lubricant additive whose use in lubriunitycating compositions will contribute particular AS indicated in the foregoing b ad statement noncorrosion properties, antioxidant properties, of h inventifin. the materials With which 5 metal-deactivating propergies, mi i propinvention is concerned can be best and most aeerties, and high oiliness to a lubricant blend wratclv defined by having relerence to their containing h it mode of preparation. In its broadest aspects the Other objects and advantages of this invention 5 invention Confiemplates p ct resulting from will become apparent as the description proceeds. the reaction of a metal and 81111111 COIltaiIlinE To the accomplishment of the foregoing and l w a P p us nd Sulfur containrelated ends, this invention then comprises the mg Organic compwnd- This latter Class f matefeatures hereinafter fully described and partice mat rials with which the metal ulafly pointed t in th shims, t following and sulfur containing reagent is caused to react description setting forth in detail certain illusfall n two broad classesflizl trative embodiments of the invention, these being 'IhOse Organic mp unds which are the reindicative, however, of but a few of the various action P 1 an Organic mp nd and a ways in which the principle of the invention may P p s d Sulfur containing ts he m class is preferred for use.

Broadly stated this invention comprises B. lhose organic compounds which contain viding; phosphorus and sulfur in chemical combination I. The organic material containing phosphorus, either in their Bats-rally Occurring State D sulfur, and a metal in chemical combination propared by means other than the preferred produced by treating a phosphorus and sulfur concedure indicated below.

The reaction products which comprise the phosphorus and sulfur containing materials of the preferred class A above can best be identified by having reference first to the various organic compounds which may be utilized in the stated reaction; and then by having reference to the various phosphorus and sulfur containing reagents which may be reacted with such organic compounds.

Accordingly for an indication of the nature 01 the organic compounds which have been found best suited for use in the indicated reaction and illustrative of the broad class of organic compounds thus usable, reference may be had to the following table:

TABLE I ORGANIC COMPOUNDS Acyclic and carbocyclic compounds I. Hydrocarbons Saturated, straight and/or branched chain,

hexane octane isooctane decane hexadecane Olefinic, diolefinic, triolcfinic, aeetylenic, dlacetylenic octadecene wax olefin dodceene polymerized isobutene amylene ethylene acetylene Polymethylene, cyclic oleflnlc, cyclic diolefinie cyclobexene methyl cyclohexene bicyc ohexadiene Aromatic, aikylated aromatic, poly-nuclear aromatic benzene warylated benzene diamyl benzene octudecyl naphthalene II. Halogen derivatives Cl, Br, I, F, or mixed halogens lauryl chloride octadecyl bromide pchloroamylbenzcne chlor wax Mono, di and polyhalogenated p, -dibcnzyl dichloride aromo-p chloro benzene polychlor naphthalene III. Oxygen derivatives-Monohydrlc A. Alcohols, saturated monohydrlc methan cyclohexanol methyl cyclo ntanol lauryl aicoho stcaryl alcohol Alcohols, unsaturated monohydric oleyl alcohol cinnamyi alcohol i'uryl alcohol phen-ethyl alcohol I Alcohols, unsaturat d-oleiinic, dioleflnic methyl cyclohexadienol 9,12octarieeadienol Alcohols, unsaturated acetylenic allyl alcohol Alcggols, hydrcaromatic, saturated and unsaturated as a re dimothyl cyclopcntanol phcnyl cyelohexanol diamyl cyclohexanol Alcohol aromatic Phen l paiaflinic p enyl ethyl alcohol wax Yhenyl-pmpanol buty pheny carbinol Alkylphenols, substituted phenols Phenols. naphthols p-phen ylphenol alpha naphthol cresol hytdroquinone ea ec dibutyl phenol t-butyl phenol octylphenol amylthiophenol laurylthiophenol sulfurized wax phenols condensed wax phenols p-chlorophenol l-bromo-a naphthol Oxyphenyl paraiiin alcohols p-hydroxyphcnyl stearyl alcohol 2,6 diamyl-4-betahydroxycthyl thiophenol Alcohol derivatives Metal salts, alcoholates Sodium triphen l silicolatc Sodium, potass um, calcium, or aluminum alcohnlates Calcium wax-Phenolate Sodium laury thlophenolate Ethers, simple and mixed, and thloethers oetodecylphenyl ether lauryl sul. de p-hydroxyphenyl ether condensed wax-phenyl ethers sulfides Esters of mineral acids di-mcth l cyelohox l dithlophosphate trilaury thiophosp ate waxylated phenol benzene sulfonate Esters of or amc acids octyl di auryl suocinic acid methyl ricinoleate dibutyl gallate Sulfur derivatives sulfurized butyl henol sulfurized oleyl a cohol p-thiophenyl henol Selenium and tel urium compounds octadeeyl- -hydroxy phenyl seleuide dioctyl tcl uride Nitrogen derivatives p-hydroxy phenyl pyridine dimethyl amine octyl phenol cycloheranol amine Phosphorus derivatives trilauryi phos hine phenyl diocty phosphonic acid tributyl phosphite Crfinpounds of As, Sb, Si, B, Si, Ge, Sn, Pb, Zn. Hg,

5;, etc. p-triethyl tin-phony] dibutyl silicol oetadecyl arsinic acid dicthyl silicon dioleyl ester B. Aldehydes Paraffin and cycloparaifin series dodecyl aldehyde methyl cyclohexylal oenanthyl aldehyde stearyl aldehyde Halogen derivatives 4-chloro-butyral p-bromo cinnamic aldehyde trichlorobutyraldehyde beta-phenyl-aldol Condensation products phenol-butyral condensates c'esol-luiural condensates, Sulfur derivatives polymeric acetaidehyde sulfurized benzaldehyde beta thiophenyl acetal thiophenol-formal condensation products Nitrogen derivatives hemmethylenetetramine il-gctadegege amide eny y rezone Oletflric aldehydes citronellal rhodinal geranial tiglic aldehyde Acetylenic aldehydes aionf'lpropiolic sldeh de d ecyliropiolic al ehyde Aromatic al ehydes benzaldehyde triphenyltrithiane p-chlorobenzaldehyde J. Ketones Paraflin and cycle-paraffin series caprinone laurone stearone iso horone azo acne methyl pentadecyl ketone Halogen derivatives methyl dibromoheptadecylketone methyl chloro-nonylkctonc Alkyl ethcrs dipropylketone orthohcxyl ester Ketonc halides dichlorocaprylone methyl t-butyl diehloromethane Sulfur derivatives Pinacoline thiolic anhydridc thioacetone, condensed trithiolaurone Nitrogen derivatives methyl butyl kctone phenyl hydrazone dicaproneamine Olcflnic and dioleflnic ketoues mesityloxide phorone camphorone Acetylene ketones aeetyl oenanthilidene dodecyl oenanthylidene Aromatic ketones anthraquinone naphthoquinone Aryl paraffin ketones dibutyl aeetophenone Michler's ketone wax naphthylketone trlolein trimyristin Glycerol nitrogen derivotiva t Dihydroxy aldehyde:

n laldeh do D Wig: 7

nes dihydrorydccylrncthyl ketone v-w H o dialdehydes ling! chloromolonie dialdehyde Hydroxy diketones hydroxy methylene henzoyi acetone Dihydroxy corhoxylie acids o-hydroxy valero-lnctone sym. dlhydrory auiaic acid Amino-hydroxy curboxylio acids mamino thiolaetie acid Monohydroxy dicarboxylic acids glhenylsteoryl maleic acid ydroxy malonic acid (Eydroxy suecinie acids Aid icarboxyiic acids Kcto-dicarbox lie acids dietoaze aic acid Urie acid-Ureldes 'lncarboxiylic acids c alcohols arbohvdrntes. Celiuloses Carbonic acid and Thiocarbonic acid ethyl thiocarbonate cetyl dithiocarbonate lauryl thiocarbimide Chlorine derivatives p. chloroheuzyl xanthate Sulfur derivatives Amide derivatives Urea, ureides. hydrazine, azines Sulfur derivatives of carbonic acid Sulfur derivatives of urea Guanidine and its derivatives N itriies and imides of carbonic acid Cyanogen and gen derivatives of carbonic acid Cyanogen and ogen derivatives of carbonic acid Cyanogen and sulfur derivatives of carbonic acid Cyanuric acid-amides Nitrogen Derivatives 1. Amines, rimary, secondary, and tertiary kyl amines VIII.

Aniline inorganic acids Diammes and polyamines Pheoyl nitrosaminea Ammonium bases Nitro eornpormds Nitroso compounds Hydroxylamines Dlazo compounds Azoxy compounds Azo compounds Hydrazine compounds IX. P As. Sb, Sn, Bi, B, Si compounds Phos hines, arsine, stiblne com unds alogen, hydroxyi, derivat vcs Phosphorous, orsenous, stannous com nods Halogen, sulfur hydroxyl, derivatives Phosphoric, arsenic, boric, silicic acid compounds Ortho, meta, pyro, acid derivatives Metal compounds Metal allryls, aryls Compounds oi Zn. Mg, Sn, Pb, Na, Hg, and Ge Metailo-orgunrc derivatives Sulfur compounds Mcrcaptans, thiophenols Sulflmc, sulfcnic. and sulfuric acid derivatives sulfides, disulfldes, poiysulfides Suifoxides. suifones Animal substances Proteins, aibumcns Amino and imino acids Hydroxy, thio derivatives Gluoo rotcins Phosp oproteins Enxymes, ierments Biliary products Heterocyclic compounds 1. Ethylene oxide homologs Ethylene sulfide homologs Ethylene imine homologs Diazomethane homologs 2. Trimethylene, oxide, imine Betaines Methylene urea, methylene thiourea 8. Furan, thiophcn, selenophen, pyrrole nuclei Halo, nitro, amino, and allgvl derivatives Alkyl-phenyl derivatives Alcohol, amine, aldehyde, acid derivatives Nitro. nltroso, oxy derivatives ss y-rem XII.

Preferred organic reactants for reaction with P381! reagents, such as P285 are:

Hydrocarbon compounds of olefinic character of the related non-olefinic compound, such as:

Wax oleflns C1: to Can Dodecene Cetene, octadecene Melene, etc.

'Irilsobutylene, polybutenes, polyisobutenes Propylene polymers Amylene polymers Mixed Ca, C4, C5 olefin polymers Styrene and polystyrene Olefin-aromatic condensates such as the simple hydrocarbon or its hydroxide, halide, mercaptide, forming the reactive olefin by the removal of hydrogen, the elements of water, halogen, hydrogen halide, hydrogen sulfide, sulfur and the like;

High molecular weight natural and synthetic olefinic structures such as rubber, Buna-S, Buna-N, butyl, butyrone, isoprene, chloroprene, rubber-like products.

Oleflnic hydroxy compounds oleyl alcohol p. hydroxy cinnamene methyl cyclohexenol 2,4-dibutenyl phenol In the following table will be found listed a number of the usable phosphorus and sulfur containing reagents which may be caused to react with any of the organic compounds listed in Table I above in the preparation of the preferred type of intermediate or starting material as per broad class B previously identified.

TABLE II PHOSPHORUS AND SULFUR CONTAINING REAGENTS Phosphorus and sulphur compounds Compounds of phosphorus and sulphur alone Phosphorus disulfide-P3Se (or PS2) Phosphorus trisu1phideP4Se (or P283) Phosphorus sesquisulphide-PrSa Phosphorus pentasulphide Pass (or P4810) Phosphorus heptasulphide-HSr Compounds of phosphorus, sulphur and halogen Phosphorus thiochloridePSCla Phosphorus thiobromidePSBra Phosphorus thiobromide-PzSaBr4 Compounds Of phosphorus, sulphur and oxygen Phosphorus sulphoxideP4S4Oa Compounds of phosphorus, sulphur and elements other than oxygen or halogen Phosphorus thiocyanate-P (CNS) 3 Reagents containing elements equivalent to phosphorus and/or sulphur.

Compounds of phosphorus and equivalents of sulphur, e. g., Se, for example PzSe PzSe: PzSes As representative examples of metal and sulfur containing reagents which may be caused to react with any of the phosphorus and sulfur containing organic compounds of Table I above, or any of the reaction products resulting from the reaction of any of the materials listed in Table II above with any of the reagents listed in Table III below, reference may be had.

TABLE III Heavy metal compounds tin sulfide lead thiocarbonate 10 Sulfonates potassium myronate potassium halomethyl sulfonates sodium wax-phenyl sulionate 5 barium cetyl phenyl sulfonate fig g gigig sodium hydroxy methyl sulfonates molybdenum sulfide The foregoing examples of organic compounds tungsten ulfide and reagents is illustrative of the use or the nickel ulfide named compounds or their equivalent in producbismuth sulfide ing the phosphorus and sulfur containing organic copper trithiocarbonate potassium trithiocarbonate potassium thiosulfate rubidium thiosulfate caesium sulflte potassium halo-metal sulfonates potassium seleno-cyanate Alkaline earth metal compounds magnesium sulflte sodium lauryl mercaptide component of the addition agent of this invention. These illustrations involve the use of reafiig g ggg gents containing both phosphorus and sulfur lithium bisumte either alone or with other elements. It is fully sodium polysulfide 15 within the scope of the invention to use either sodium Sumte phosphorus or sulfur containing organic compounds either naturally occurring or synthetic, as in Class B above, to combine with the alternate either phosphorus or sulfur containing reagent to produce a phosphorus and sulfur containing organic compound capable of forming a metal derivative and coming within the scope of the broad classification set up above under B. The methods or preparing such additive compounds for further elaboration are illustrated by magnesium sulfate the following: calcium sulfide calcium thiocyanate A. Organic sulfur compounds combined with t t m Sumde phosphorus bearing agents, such as elestrontium sulfite mental phosphorus, strontium hydrosulfide P013, P015. P8013, strontium thiocyanate P205, P001: barium sulfide reacted with: barium trithiocarbonate Mercaptans. op nols barium hydrosulfide Thioethers. R-disulfides, polysulcadmium sulfide fides cadmium thiophosphate i ph ne, thiopha-n cadmium thiocyanate Alkylated phenol sulfides zinc ulfid Thioacids, esters, aldehydes zinc thiophosphate 40 Tliocarlzonates, xanthates, thioorma es Mgiallilig 1ssulfur compounds containing organic Thionc anhydfldes' mic-amino- Mercaptides acids B. Organic phosphorus compounds with sulfur bearing reagents, as ggggii g gg g g g Elemental sulfur, CS2, COS, SzClz, SO12, sodium diamyl-thiophenolate gfg Pas Disulfides and polysulfides a g' g i ifi gi gfgg umde fi g Phosphates, PhOS- D S 52:3 i q fgg g Phosphonic acids, esters and salts Thin $212 28: P0 y Phosphinic acids, esters and salts Organic phosphines 5311733213: $32 21 btgirilgzzrbonate 55 Organic phosphine halides sodium phenyl thiocarbonate Xanthates Lecithin, cephalin, phospholipides,

phosphoproteins Among the various organic materials listed for gggili ggfi ifigg ig example in Table II above, which may be utiotassium 150% 1x anth ate c0 lized in the preparation of the phosphorus and Thiolzyanates y o sulfur containing intermediate, unusually desirdiphenyl zinc dithicphosphate methyl 'cyclohexyl sodium thiophosphate dicresyl barium thiophosphate sulfurized diamylphenyl thiophosphates acetaldehyde potassium bisulphite able results will be secured when utilizing organic compounds having a molecular weight of the order of 300. While the molecular weight of 300 or thereabout is particularly preferred because of its oil solubilizing characteristics, other compounds having molecular weights ranging from roughly 150 to 1,000 or more may be used as desired.

Essentially paraflinic hydrocarbons such as bright stocks, residuums, lubricating oil distillates, wax distillates, petrolatums, or paramn waxes may be used. Certain synthesized higher formaldehyde potassium bisulphite alkylated aromatics may similarly be used in efbenzaldehyde potassium bisulphite testing the desired compositions. In order to bring the parafllnic material into a reaction condition, it is frequently necessary to effect a preliminary reaction such as halogenation of the hydrocarbon with subsequent dehalogenation to produce the preferred unsaturated and reactive material. Similarly, the halogenated hydrocarbon may be condensed or combined with olefinic or unsaturated compounds, for example of the cyclic structure, by condensing agents such as anhydrous metallic halides, aluminum chloride, zinc chloride, ferric chloride, boron fluoride, and the like.

To effect the particularly preferred phosphorus sulfide-olefin reaction product, a hydrocarbon of uniform olefinic composition is chosen. Such a compound may be a pure olefin, obta ned for example by dehydrating a higher alcohol, such as a cetene, melene, dodecene, and the like. Similarly, olefins of uniform composition obtained by the halogenat on of petroleum wax stock and subsequent dehydrohalogenation are highly efficacious in producin the desired phosphorus sulfide compositions. I prefer particularly to employ a uniform composition olefin product having at least 20 carbon atoms in the molecule of which at least 15 or more carbon atoms are in a straight chain structure. Such olefins are preferably obtained by the halogenation of long chain wax compositions and the subsequent dehydrohalogenation of the halogenated products obtained. In the preparation of the preferred phosphorus sulfide olefin compositions. it is recognized that the mono-olefins react differently from the diand poly-olefins, The compositions I particularly prefer are the mono-olefinic compounds such as are obtained by the halogenation of waxes to produce an essentially mono-halogenated wax, followed by the dehydrohalogenation of such a product, or the essentially pure mono-olefins obtained from mono-halogenated wax separated from the total halogenated product by fractionation followed by the splitting out of a hydrogen halide and the formation of an oleilnic long chain molecule of uniform structure.

By way of example but not by way of limitation, I shall describe the method of obtaining my addition agents from a low melting point wax of from 18 to 24 carbon atoms per molecule. The wax is halogenated to a halogen content of from 8 to 12 per cent- The preferred halogen is chicrine. The crude halogenation mixture will comprise some unchlorinated wax, mostly monochlor wax and some more highly chlorinated waxes. Chlorination of wax lowers its melting point stepwise inversely as the degree of chlorination. A monochlor wax will melt lower than the like unchlorinated wax. A di-chlorinated wax will have a lower melting point than the monochlor wax. The unchlorinated wax may be separated readily from the crude chlorination mixture by melting point differences, using sweating, or selective solvent extraction at various temperatures.

A solution of the crude chlorination mixture may be formed with acetone. At about 70 F., the chlorinated waxes will be in solution, while the unchlorinated wax will not dissolve and may be separated by settling, centrifuging, or filtering. The solution may be chilled to precipitate the monochlor wax. Thus the monochlor wax may be separated from the polychlor wax employing the same methods as those outlined for separatfing unchlorinated wax from the chlorinated wax mixture.

The monochlor wax thus obtained is substantially free of unchlorinated waxes or more highly chlorinated waxes and may be converted to the corresponding olefin by removing the chlorine as hydrogen chloride, thus producing a double bond. To prepare the olefin, the monochlor wax may be heated for a period of from one minute or less to five hours, with one tenth of its weight or more of lime, at temperatures between 200 F. and 550 F. The olefin may be formed by removing the hydrogen chloride by heat alone or by other reagents or processes, although the color of the resulting olefin may be darker than when lime is used. After dehydrohalogenation, the lime or other basic dehydrohalogenating agent is removed from the resulting olefin by the usual means, such as by filtering.

The theoretical iodine value for an oleflnic hydrocarbon having the formula C2sH5c is 72.6. The iodine value of the olefin prepared as described is about 72.

It should be pointed out that the olefin made as described is a definite type of compound having the structure:

When prepared from a parafiin wax, R is an aliphatic group containing from 1 to about 20 or more carbon atoms. The sum of the two Rs should be between 10 and carbon atoms. When the olefin is prepared from a wax, a highboiling mineral oil, or mixture of wax and mineral oil, a specific type of structure is always obtained. In phosphorus-sulfurizing this type of compound, the Pas]! reagent adds on to the double bond and is not substituted for hydrogen, as is shown by the fact that in the PIS reaction practically no H28 is formed. This fact makes it possible to prepare a definite type of compound in contrast to the heterogeneous mixture which is obtained when a saturated material, a cracked petroleum derivative, or a polymerized olefin containing many types of unsaturates is treated. The advantages of the former, due to its purity and homogeneity of composition, are many.

As an indication of the manner by which a phosphorus and sulfur containing intermediate, useful in the manufacture of the products of my invention by the further reaction therewith of a metal and sulfur containing reagent may be prepared, reference may be had to the following example.

EXAMPLE I One hundred parts of the olefin prepared as described above are chemically combined with from 6 to 30 parts of phosphorus sulfide, preferably from 12 to 24 parts of phosphorus pentasulfide. This is accomplished by heating and stirring the olefin with increasing temperature until a temperature of about 200 to 250 F. is attained. In this temperature range the first quantities of phosphorus sulfide are added. This early addition of phosphorus sulfide is a precautionary measure to preclude polymerization of the olefin. Thus, as the olefinic double bond becomes more reactive with increasing heat, the phosphorus sulfide will add thereto instead of permitting an olefin polymerization to take place. Heating and stirring are continued with additional increments of phosphorus sulfide until a temperature of approximately 340 to 360 F. is attained. By this time the phosphorus sulfide has begun to react thoroughly, and all the phosphorus sulfide should have been added. The temperature is maintained in this range of 350 plus or minus 10 F., until the phosphorus sulfide has apparently gone into thorough and complete solution. This is accomplished with active stirring in from to 30 minutes. Under certain conditions, however, longer periods of time may be required. Additional beneficial effect is obtained if an inert atmosphere is maintained over the reacting olefin mixture, such as by maintaining a dry gas (CH4) atmosphere or .a nitrogen atmosphere over the reacting mass. The reaction with phosphorus pentasulfide is quite rapid, and almost immediately the olefin-phosphorus sulfide product has the sulfur firmly bound, such that'a solution of the reaction prodnot in a light hydrocarbon does not give a copper strip positive test. The phosphorus sulfideolefin product may be cooled and discharged at once: however, it has generally been found desirable to continue the heating period with an inert atmosphere over the reaction mass with stirring for approximately V hour, in order to ins re a com l te r action of the phosphorus sulfide, both of the phosphorus sulfide not completely in solution and of the phosphorus sulfide in physical solution in the olefin or olefinphosphorus sulfide product. The product resulting from the foregoing reaction may be refined by blowing with an inert gas, for example, to improve the odor of the product, by treating with active clays o improve the color of the product, and/or by treating with chemical clays such as caust c impregnated clays to improve the color of the product and at the same time remove a small quantity of the reactive material which apparently causes sludge formation. It has been found particularlv desirable to treat the crude phosphorus sulfurized product with a neutralizing agent such as fullers earth or the equivalent, such as bauxite, lime, or caustic at temperatures between 200 and 300 F. for such a period of time as is necessary to effect a partial reduction in the free acidity usually found in the crude phosphorus sulfurized olefin product.

As will be pointed out hereinafter in greater detail, one feature of the present invention is the extremely high concentration of sulfur in the end products which are especially desirable for use as lubricant improving agents, and the retention of substantially all of such sulfur content, comprising 80% or more of the S:P ratio in the P18? reaction product, in the preparation of the metal derivative which comprises the end product. In certain instances where the sulfur concentration in the intermediate, 1. e. the phosphorus and sulfur containing organic compound which is reacted with the metal and sulfur containing reagent is not at the theoretical maximum, then the latter reagent may actually contribute sulfur in addition to metal to the end product.

I am aware of the fact that certain prior art workers have prepared phosphorus and sulfur containing organic compounds by the reaction of an unsaturated organic compound with a phosphorus and sulfur containing reagent and such materials have been proposed for use as lubricant improvers. Materials of that character are, however, highly acidic and it hasv accordingly been proposed also to reduce the acidity of such acidic materials by means of alkali hydroxides and the like. The neutralization or partial neutralization when accomplished by the use of a hydroxide, oxide or carbonate or even certain metal sulfides removes a very substantial amount of the sulfur from the phosphorus sulfide reaction product, and to the extent that sulfur is 14 thus removed, the product is rendered less effective and less desirable.

I have discovered that a high content of metal may be introduced and a high content of sulfur maintained in the compound, producing a composition having outstanding thermal stability, storage stability, oil solubility and detergent properties in addition to the desirable characteristics heretofore disclosed, if the metal derivatives are prepared in a prescribed manner by the action of the metal and sulfur containing reagents listed above either in solid form, as hydrated solids, or as aqueous or aqueous-alcoholic solutions. The metals whose sulfur compounds are most active in this connection are the alkali metals and alkaline earth metals. may be used as sulfides, polysulfides, thiocarbonates, xanthates, etc. However, I prefer the active alkalies and alkaline earths, such as sodium, potassium, lithium, calcium, barium, magnesium, strontium, etc. as sulfides, hydrosulfides, polysulfides and the like. By this means I have sucereded in preparing oil soluble phosphorus sulfide hydrocarbon products, such as PS-Olefin compounds, having up to six equivalents of metal combined; however, derivatives with from 1 to 3 equivalents are preferred, per molal unit of P285. For example, I have prepared oil soluble, stable, alkaline, non-turbid compounds having the em= pirical composition NaeRsPzSa, using sodium sulfide as a rragent, wherein the high metallic content is apparenty in complete organic combination and the sulfur content is essentially in agreement with the formula shown and not appreciably reduced as would invariably be the case in the preparation of a similar type of compound from caustic soda NaOH, or as would generally be the case when an aqueous-sulfide solution were used as a reagent.

It is often desirable to prepare and use heavier or polyvalent metal derivatives such as the aluminum, indium, tin, titanium, chromium, copper, lead or other metal derivatives in lubricating compositions. When such a derivative is not available by the direct reaction of the metal sulfide, polysulfide, etc. with the PS reaction product, the compound can be prepared by metathesis with the availablealkali metal derivative. By reacting a salt of the desired heavy or polyvalent metal with the sodium derivatives, for example,

the particular heavy metal derivatives may be prepared without substantial change in the content of combined sulfur.

The preparation of the high sulfur content metal derivatives of PS organic reaction products, as illustrated in the following examples, is preferably carried out at temperatures in the range of ZOO-300 F. in an inert atmosphere and under pressure to avoid HzS loss, using the hydrated crystalline solid compounds, the finely divided non-hydrated solids, or, less preferably, concentrated solutions of the metallic reagent in order to effect the formation of metal derivative in a short time and with a minimum or controlled hydrolysis and little or no HzS loss. Long periods of heating over several hours, particularly above 250-300 F. with water present, are detrimental to the composition and are to be avoided. By way of illustration and not by way of limita tion the following examples are presented:

EXAMPLE II One molal part of PSO-Zl having a neutraliza- Other metals parts of olefin prepared as described in-Example I, mixed with an equal weight .of light oil as a diluent and containing 2 cc. of a silicone oil solution as an anti-frothing agent is heated and stirred in a sealed vessel to 200-230 F. in an inert gas (N2, CH4, etc.) atmosphere and 20 pounds pressure. 0.5 mole of sodium sulfide nonahydrate (NazS.9Hz) is heated and dissolved in its hydrate. The sodium sulfide solution is added to the reaction system at about 220230 F. No dangerous frothing or less of material either liquid or gas, is encountered due to the action of the anti-frothing agent present. The temperature is quite rapidly raised to 300 F. The reaction product is a clear dark liquid which is filtered through paper and recovered as a clear oil-soluble material. The total time of reaction is of the order of 30 minutes. If the heating is protracted and if large quantities of aqueous solution are used the product may have a higher titratable acidity after the reaction than before. By the method outlined, the product has a low titratable acidity or may have excess alkalinity. The product thus prepared has. been analyzed and tested as further shown below.

EXANIPIE in 'over a period of about one-half to one hour, to

300 F. and the product clarified by centrifuging or by filtration through paper. This all soluble product is further described below.

EXAMPLEIV One molal quantity of PSO-21 as described above in Example II, diluted with an equal weignt of diluent oil and containing approximately one part per thousand of silicone oil solution as an anti-irothing agent is heated and stirred in an atmosphere of nitrogen gas at pound pressure to about 200 F. One molal partpf sodium thiocyanate, NaCNS dissolved in cc. of boiling water is added at 200-250 F. or thereabout. Water appears to be retained in the reaction mass to about 300 F. in which range water is eliminated as a vapor. The product is clarified by centrifuging and/or filtering. The oil solution of this additive is bright and clear. Further tests are described below.

EXAMPLE V With sodium sulfide as a reagent, the metal derivative of the compound prepared in accordance with Example VI has been prepared in which the sulfur and phosphorus sulfide-methyl ricinoleate reaction product diluted with an equal weight of a light oil has been brought into reaction with the sodium sulfide hydrated crystals at temperatures between 200 and 250 F. for a period of from V to 1 hour. The resultant product has shown a very minute diminution in sulfur content, corresponding to not over /m per cent on the basis of the analyses, which 16 values are well within the range of probable error in the method of analysis for sulfur combined in such organic additives. The sodium derivative of the diluted sulfur and phosphorus sulfidetreated methyl riclnoleate showed a 4.2 per cent ash value which corresponds to 1.37 per cent of sodium which indicates that approximately of an atom of sodium has combined with the sulfur and phosphorus sulfurized methyl ricinoleate to form a compound having approximately the composition NaR4S4P:S5. Blends of this metal derivative in a 170 pale oil showed a high thermal stabilitv and gave clear stable solutions in the oil. While the phosphorus sulfide and sulfurtreated methyl ricinolea e product when blended in an oil prod"ced a sludge in 16 hours at 325 F. and a depreciation in optical density of 624, the above-described sodium derivative in a 1 per cent blend gave a clear light oil with no sludge after 16 hours at 325 E, which oil showed an optical densty depreciation of only 140.

The compounds prepared as illustrated above have retained their sulfur content to a major degree and within the range of 80% or more of the original 8:? ratio, and on extended treatment with the metal sulfur-containing compounds. have regained the modest initial losses of combined sulfur.

Analysis of Ps0-21c and sodium-sulfide derivatives [Prepared according to Example 11] This demonstration of sulfur maintenance and sulfur build-up with metal sulfides is to be contrasted with the loss shown on forming the NaaPSO 21 derivatives from aqueous or alcoholic NaOH or the like.

A more striking demonstration is of the action of the metal sulfur compounds with no free water in the formation of superior additives of the metal-PSO type, in which the sodium derivatives prepared from NaOH and from NazS are compared on a series of compounds synthesized under identical time and temperature conditions as shown in Example II.

Atomic Neut. Percent Quant.

N o. 804 Ash Sodium Found It is clearly shown that the extent of metal derivative formation is practically equivalent 17 when using the metal sulfides or the hydroxides, however the advantage of lower free acidity or higher alkaline reserve is regular and pronounced in the water-free sodium sulfide series. This excess alkalinity is a clear and desirable advance in the compounds of my invention.

Underwood tests carried out under conditions of accelerated corrosion more fully establish the superiority of the metal PSO derivatives prepared from the sulfur containing metal compounds. In these tests the oil is subjected to the Underwood test conditions plus:

(1) Progressive addition of corrosion accelerator (soluble lead naphthenates) equivalent to .025 per cent of lead as PbO every 2% hours,

(2) The injection of air over the hot oil bath at the rate of cu. ft./min.

Underwood data In the compositions below, the base to which the stated percentages of the identified materials were added consisted in each case of an SAE 20 Mid-Continent base solvent refined oil plus 0.5% methyl dichlor stearate.

1. 2.50 per cent blend of reference additive.

PSO 21-0, or metal derivative of PS 21-C equivalent to 0.15 per cent added theoretical sulfur.

Corrosion (Time in Induction Loss Hrs.) Time, Hours 0mm) cdTAg Cd-Ag Cu-Pb l0 15 20 A. PS0 21-0 15.0 15.0 0 0 0.9 0 02.75 B. PSO2l-C-Na1/Na0lEL- 14.0 15.0 0 0 0.8 0 2.55 0. PS0 2l-C-Nal/Naa8.-. 20.0 19.5 0 0 0.2 0 0 0.1 D. Sullurized Olefin 12.0 12.5 00.61.65 0 1.5 4.5

2. 1.25 per cent blend of PSO-21-D or metal derivative of PSO-21-D equivalent to 0.075 per cent added sulfur.

It is evident from the tabulated data that the sodium sulfide hydrate derivatives are markedly superior to the sodium hydroxide derivatives and far superior to the PS0 materials alone as metal deactivators and corrosion inhibitors. The metal derivatives obtained from sulfur containing radicals generally show a real improvement as corrosion inhibitors. The results here show a new high order of activity when the results are compared with a commercial inhibitor (sulfurized olefin) considered a superior product in its field. When one considers that marketed commercial lubricating oils show a 7 40 hour induction time on this test, the outstanding effect of the preferred metal-PSO derivatives becomes pronounced. Thus, with as little as .038 per cent added sulfur as the preferred NazS-PSO derivative the resultant oil blend has an induction time equivalent to that produced by 0.15 per cent sulalone become turbid in from 2 to 45 hours.

18 fur as sulfurized olefin, the reference anticorrosion additive.

These metal derivatives of the PS-hydrocarbon have outstanding thermal stability. Blends of the metal PS-hydrocarbon additives in oil remain clear and bright on exposure to sunlight over a long period of time whereas PS-hydrocarbons On exposure to temperatures or the order of 325 F. for 16 hours or longer, the PS-hydrocarbon blends sludge badly. giving a dark oil and depositing a tenacious black gum on the containing vessel. With these metal derivatives, not only is a clear stable solution obtained in oil, but the solution is also outstandingly stable to the high temperature thermal test-no sludge or gum is formed from our blends in which an appreciable amount of metal is bound in the molecule and very little color depreciation is observable after the 16 hours test. This characteristic of high thermal stability is clearly a. mark of an additive of outstanding value for the present high temperature, high speed engine lubricants. The compounds or particular value in this regard are the metal-PS-hydrocarbon derivatives having a high sulfur content such as have been illustrated above as being prepared by the prescribed action of metal sulfides, hydrosulfldes, polysulfldes and sulfur containing organic compounds on the PS- organo reaction product.

In order to establish a reproducible and factual measure of this outstanding characteristic of high thermal stability, I have prepared 1 per cent blends of the additives in a light pale) Mid- Continent solvent treated oil which is sensitive to oxidation. The color value or optical density of the sample is determined on the Klett-photoelectric colorimeter using the green filter #54 and setting the value of the neutral 170 pale oil alone as zero. The color value is taken of the additive blend before thermal treatment and after given intervals of exposure at 325 F. in a constant temperature oil bath. The increase in concentration of color bodies or the change in optical density on thermal tests is a progressive measure of the breakdown (sludging) tendency of the oil blend. and is far more sensitive and rapid than the Underwood Test.

Optical Density Values after hours at 326 F.

Series C PSO 21-5 122 520 "1,200

2 MNal/Nafi--- 84 103 720 1,075 "2,000

2 PS0 21-5 Nal/NaOH.. 92 195 1,000 1,91)

2 P 89 2 l Na2/I Ta18.-. 85 113 217 365 855 1,406

2 1i02 1-5 Na2/Nm8(o) 91 117 222 350 815 1,245

2 MNQINaOHH 86 127 250 990 2,075

Bind formed and test terminated.

(0) F0 owing the preparation of Example III.

It is clearly demonstrated above that the derivatives prepared from metal and sulfur containing compounds have a uniformly better initial color than the PS-hydrocarbon product and quite generally a better color than the similar derivative prepared from NaOH. Whereas the PS0 blends are sludged heavily in less than 16 hours at a color value as low as 500, the metal derivatives and particularly the high sulfur metal derivatives show unusual color stability (slight change in optical density) and outstanding resistance to sludging. The color stability increases with increasing metal content. The particular superiority of the metal sulfide series over the comparable metal hydroxide derivatives is shown in the Series C tests above. While the PS0 base blend was sludged at 16 hours, the NM series was stable through 32 hours for Nal/NaOH and through about 48 hours for Nal/NazS, and the Na: series was stable through 48 hours for ZNa/NaOH and through 80 hours'r'or 2Na/Na1S prepared according to Example II and even more stable, through 80 hours, as prepared according to Example 111 from the crystalline hydrates. This is recognized as a characteristic Oil Sump Temp, F 260 Jacket Water Outlet 185 Jacket Water Inlet 175 Speed, R. P. M 2750 Load, H. P 19 Fuel '16 octane, 2.5 ml. TEL/gal. Duration 5000 miles for breakdown The base oil is a blend of Mid-Continent solvent treated stocks SAE 20 grade with 0.4 per cent methyl dichlorstearate added as an oiliness agent.

of the metal-PSO derivatives in which excess alkalinity or alkaline reserve is present. Since I have shown above that the metal sulfur-containing compound and particularly the reaction of the hydrated form is particularly effective in producing such excess, or reserve alkalinity, such compounds are illustrative of the particularly preferred forms of the invention.

A number of the preferred additives prepared according to the methods shown above and having a high combined sulfur content due to the 75 Lubricant 2. 6'7 hour Chevrolet heavy-duty runs under the following conditions:

Oil Sump Temp. "F 280 Jacket Water Outlet F 200 Jacket Water Inlet Engine R. P. M 3,150 Load H. P 30 Hours 67 Fuel 74.2 octane, 2.5 ml. TEL/gal.

SAE 20 min. Oil-H14 MDB (The base oil is an SAE 30 grade blend of Mid- Continent solvent treated stocks plus 0.4 per cent methyl dichlorr-stearate as an oiliness agent).

22 acidity developed in the oil during the period of use,

2. Resin content as a measure of the bulidmn Per Cent Per Cent Demerit Com) Ring Additive sion Wt. Gap

Sulfur Additive Rating Loss wear A. PSO21-NazS stabilized-.- 0. 25 4 25 14 0.100 0.010 B. 8441 2. s is 2. 110 0. 020 0. Poem Suli. Olefin 0. 25 f: g 14. s o. 200 0. 010 12. $4.01 Suli'. F. acid ester.-.. 0.15 3:2 1. 632 0.000 E. 244'1 Suit. 1. acid ester-.-. 0. 3' 3 13 0. 008 .000 r. P 105-3 Sulf. olefin 0. 25 3- 8 11 0.150 .005 a. r 105's Suit. 1. acid ester. 0. 25 fig 17 0.122 .008 H. P 105-3 a0 15 1. 45 .005

per cent.

'2 Commercial-detergent recommended (or heavy duty use at 2.15 per cent. '3 Commercial antioxidant recommended [or heavy duty use at 2.9 per cent.

It is clear that the preferred polyfunctional 25 of hydrocarbon oxidation products in the oil duradditive of my invention gives greater corrosion protection and higher detergency than the reference additives which include, among other combinations, combinations of commercial antioxidant and detergent additives. The mechanical condition of the test engines is important, both detergency and bearing corrosion are accurately evaluated in the diversified mechanical systems used.

However, a further significant qualification of the lubricant is in the condition of the oil drained ing use,

3. Viscosity increase as a measure of the buildup of higher molecular weight condensation or polymerization products and/or suspended solids from fuel or lubricant,

4. Iron content as a measure of the extent of corrosion of the engine parts during use.

Each of these criteria is of value in assaying the oil; the combined tests serve as a rather critical survey of the degree of deterioration of the lubricant oil.

Analysis of used engine oils from 5,000 mile runs at 260 F.

(SERIES 1, ABOVE) [Base oil=SAE 20 Mid-Continent solvent treated mineral oil plus 0.4 per cent methyl dichlor-stearate.]

Ncut. Per Cent 210 F. Per Cent Addmve Engme No. Resin Vis. Incr. Iron Chev 7. 4 20. 3 26. 9 0. 102 Suliurized olefin 0.15% S 6.4 21.0 22. 9 0.137

Pontiac- 7. 4 20. 4 146. 5 0. 11 Chev 4.2 17. 5 45. 2 0. 07 Sulfurized fatty acid ester do.. 4. 4 13.1 16.3 0.07 0.15% S. golntiac ev so i i sstabilized PS0 21 1 )l 2. 0 5. 3 7 o u M Pontiac 3. 3 8. 3 13. 2 0.07 Chev 4. 2 5. 0 6. 0 0. 05 PSO-2l-Na2.0 0.15% S do- 5.5 5. 3 5. 7 1 0.04 Pontiac. 7. 7 6. 7 10. 8 0. 03 Chev 4. 3 2. 0 3. 0 05 PSO-21-Na2.0 0.25% S do....- 6.3 4.7 8.0 .05 Pontiac. 6. 1 6. 1 10. 4 02 above.

from the engine at the end of a test run. A poor lubricant oil is markedly deteriorated and has left a dirty, corroded engine. Certain detergent-type oils are generally mildly corrosive such that the engine is clean, the dirt and corrosion products dispersed and carried away, leaving an unsludged and generally mildly corroded engine. An oil having antioxidant properties and metal deactivating properties may show excellent oil stability, but the engine is prone to be dirty. Now with a single multifunctional additive which is efiective in detergent and antioxidant action, engine results have been obtained which are outstanding for engine cleanliness, low corrosion and low wear and simultaneously producing a used oil which has been but slightly deteriorated in use.

The following table presents the analytical data In every category of comparison the used oil containing an additive within the scope of the present invention shows marked superiority to the reference oils. Together with the engine ratings shown above, the data demonstrate a new high order of activity as detergents and antioxidants for the preferred polyfunctional additive having a high sulfurzphosphorus ration of this invention. 7

In practically every lubricant application the oiliness or load carrying capacity of the lubricant is of high import. The lubricant oil blends containing the stabilized metal derivatives of phosphorus sulfide treated hydrocarbons prepared by the action of the preferred metal and sulfur containing reagents have shown high oiliness and load carrying capacity. For example, an SAE 20 mineral oil having no additive showed a pressure wear index on the Shell 4-ball" tester of 2.8 and a seizure load" value of 28 pounds, while this same base oil containing 0.15 per cent 23 added sulfur as the sodium (NaaS) stabilized phosphorus sulfide olefin product had a pressure wear index of 6.1, an increase of 3.3 and a seizure load of 60 pounds, an increase of 32 pounds, demonstrating the desirable lubricant improving characteristics of the preferred additive.

The foregoing examples illustrate the preparation of materials having high sulfur content comprising the metal derivatives of phosphorus sulfide treated hydrocarbons, particularly phosphorus sulfide treated wax olefin, in which preparation a high sulfur content is maintained at the phosphorus sulfide reactant ratio or near (within 80% of) that value by the action of organic or inorganic metallic sulfides, polysulfides, and the like in forming the metallic derivatives under conditions of minimal hydrolysis and H28 loss. The type of reaction by which a high sulfur content is maintained in the reaction products of a phosphorus sulfide treated material of organic origin for which it is desired to form a metal derivative may be applied to products other than the phosphorus sulfide-olefin or even to other than the phosphorus sulfide treated simple hydrocarbons of aromatic, cycloparaifinic or parafiinic nature. For example, the phosphorus sulfide reaction products with aliphatic alcohols or aromatic alcohols comprising the phenolictype compounds are similarly highly benefited by the use of the metallic sulfur-containing compounds as reagents in forming the metallic derivatives, by which means the original sulfur content is essentially maintained and may, under certain circumstances, be augmented. Thus, the esters of thiophosphoric acid produced by the action of phosphorus sulfides, particularly phosphorus pentasulfide, on alcohols of the higher alkyl series such as octyl, dodecyl, octadecyl alcohols, and the like, or alcohols of the cycloparafiinic series such as cyclohexanol, methylcyclopentanol, methylcyclohexanol, and the like or aromatic alcohols such as phenols, alkylated phenols, alkylated. naphthols, alkylated cresols, catechols, and the like, in which from one to three hydroxyl radicals are introduced into combination with the phosphorus sulfide moity to form a completely esterified product or a partially esterified product having residual acidity. In each of the products of this type, whether it be a so-called triester of thiophosphoric acid or an acid ester of thiophosphoric acid, or the like, the product of reaction has a minor to an appreciable amount of free acidity. A product of this type is unstable and corrosive to metals such as copper. iron, lead, and the like. Their stabilities are very considerably less than those of the corresponding metal derivatives, particularly in the presence of iron or other active catalytic metals. The thiophosphoric acid esters, will decompose fairly rapidly at temperatures above 250 F. and will retain their original composition only if storage temperatures are kept low, of the-order of F. or less. It is of particular advantage, therefore, to prepare the metallic derivatives comprising essentially metallic salts of the partially or completely esterified thiophosphoric acid by the action of metal sulfur-containing compounds such as the alkali or alkaline earth or other metal sulfides, polysulfides, disulfides. sulfoxides, thiocyanates, and the like. This reaction has been carried out using water-free metal sulfur-containing compounds to produce a metal derivative whose sulfur content is materially better than that obtained with metallic hydroxide or carbonate or even with aqueous metallic sulfides with accompanying H2S loss, and whose properties are substantially improved in anticorrosion properties, anti-sludging properties, storage stability, and the like.

The effect of the metal sulfur compounds in maintaining or augmenting the sulfur content has been demonstrated by the action of both organic and inorganic metal sulfur containing compounds upon a wax olefin-PIS, compound (PSO-2l equivalent to RaPzSs).

PS0 21 from wax olefin, diluted with an equal weight of pale oil as an inert diluent was treated with the following metal derivativeforming reagents containing sulfur:

1. Potassium ethyl xanthate in varying proportions of Kz/PSO 2. Sodium thiocarbonate as 50 per cent solution equivalent to 2Na/PSO 3. Sodium polysuifide equivalent to 2Na/PSO.

For purposes of comparison, a PS0 derivative with a potentially high metal content was prepared, using five volumes of 5 per cent alcoholic KOH as reagent, refluxing to two hours, separating the oily layer and recovering the PSO-metal derivative in a solvent-free state. The following tabulation presents a summary of the derivatives formed:

Metal-PSO derivatives with high sulfur content from RaPgSg 2 where R=waz olefin=350 mol. wt.

Molal Molal Chan Ilvlfattio 3323 gg g (tsfillflll) suing) ir Pe r Pg Cent e eory oun cut an React ant Prod Sulfur 8e bined Potassium ethyl xanthate. Sodium thiocarbonate.

. Potassium hydroxide. None.

sulfur content is effected. with certain sulfur.

compounds such as the thiocarbonates, thiophosphates, polysulfides and the like, a modest to an appreciable increase in sulfur content may be effected even in the formation of a metal derivative having of the order of one equivalent weight of metal in combination per mole of phosphorussulflde reaction product. The high sulfur compounds so prepared are particularly to be contrasted with the metal derivatives pre ared with the oxides, hydroxides or carbonates. Thus, while or more moles of KOH, in alcoholic solution, were used to effect the formation of a metal derivative, only 1.2 equivalents of metal were combined with a concomitant loss of 45% of the original sulfur content. By my method of preparation it is at once possible to produce a Prsy derivative having an appreciable to a high metal content and a retained high sulfur value or even an augmented sulfur content acting as an effective anti-oxidant and metal deactivating agent. Heretofore in bringing about the preparation of metal PS-R derivatives a displacement of the sulfur originally bound to phosphorus has been effected, such that the active inhibiting effect of the (PS) unit structure has been largely reduced or destroyed.

In some instances certain investigators have recognized that the combined sulfur content of the additive is directly relatable to the effectivecombined and the sulfur so introduced is partially or wholly active sulfur such that a copper test strip is darkened on testing such an additive at 210 F. for thirty minutes or more. The data above show that a sulfurized olefin or fatty acid ester are markedly inferior to my preferred stabilized phosphorus sulfide additive. It is clear, then, that any free sulfur used to augment the sulfur content of the additive gives the product the sharply lower merit rating of a sulfurized product compared to the preferred, non-sulfurized product of my invention which has only stable and firmly bound sulfur in essentially the ratio initially present in the Pzsy reactant without using free sulfur or an added sulfur compound. Thus an outstanding analyzable characteristic of my preferred metal, phosphorus and sulfur containing organic composition is in its having:

(a) High stable sulfur to phosphorus ratio, which ratio is at least 80 per cent of the original $22 value in the PxSy reactant and which has not been attained by the action of free sulfur or the addition of organic sulfur compounds and/or (b) An increased sulfur to phosphorus ratio 340-360 F. was taken for consideration.

I .26 which is generally attained by the action of metal organic sulfur compounds which introduce, only stable sulfur into the combination,

(0) High metal ratio in combination such that the metal derivative has high thermal stability as characterized by the above described additives having excess alkalinity, which excess alkalinity has been developed with both alkali and alka line earth metals,

or) Stably bound sulfur such that a. test blend does not darken a copper test strip exposed to the oil for 30 minutes at 210 F.

To further emphasize the difference between my compounds and those prepared from the known art, a PS-R. compound treated with 8 per cent of dry KOH for 5 or more hours at suming an organic compound of 1000 molecular weight treated with 10 per cent of P285, the PSR product will have the approximate formula R2'2P2S5=2420 g/mol. When this is treated with 8 per cent KOH dry, the KOH reactant equals 193.6 g. or 3.5 moles of KOH, giving a presumed compound of Ka-sRz-zPzSs. The analytical data for the final product show:

P= .8 per cent/31=.090

S=1.8 per cent/32=.056

K=3.0 per cent/39=.077 R=91.4 per cent/1000=.091

m a u z Summarizing the above: (1) Only 2.2 equivalents of K are in combination from 3.5 equivalents available for reaction; 2) Sulfur content has been reduced 30 per cent; (3) Excess basicity has not been developed by this methodthe product is shown to be acidwith a neut. number of 7.5.

R=82.50%+1000=0.083 or, assuming no loss of organic reactant, R 0.8 P S 2.6 Na 1.7 or

1. /56 of the total sulfur was not found incombination,

2. /39 of the total sodium was not found in combination,

3. /50 of the maximum original sulfur in combination with the phosphorus remained in combination.

The beneficial effect upon oil blends of my preferred high sulfur metal derivatives of P181! reaction products is shown in a series of thermal stability tests at 325 1". on various additives as follows:

28 from 200 F. to 300 F. for 3 hours.

Product illtered through paper and tested.

Thermal stability tests at 325 F. on PS 21 and its metal derivatives [In 2 per cent aolutioni70 pale oll.1

l siudred. I Heavily sludged.

when no metal derivative is present (No. 1) the oil blend of the P: St reaction product depreciates rapidly in color, as a measure of the degree of oxidation oi. the oil, and sludges badly. with a sulfur containing and sulfur sparing compound used in .the ratio 01'- iour equivalent weights per mole of P: S reaction product (No. 2) the oil blend has outstandingly improved stabilitythe concentration of color bodies in the oil are at first actually decreased and then only slowly built up. By comparison (No. 3)a metal derivative using 5.5 equivalents of KOH and having a large part (45 per cent) oi' the originally combined sulfur eliminated in the derivative-forming reaction is less stable than No. 2. Sample No. 3 prepared with KOH was sludged in 24 hours, whereas the compound in which the originally combined sulfur was spared or augmented was not materially darkened or sludged in the same testing time. The new composition containing both a high metal content and high sulfur content shows such clear superiority over the low sulfur derivatives as to demonstrate a new composition and a new order of activity.

The data from the foregoing table is shown in the drawing and strikingly illustrates the differences above pointed out.

Illustrative of further specific differences between the metal derivatives oi organo-thiophosphoric acids prepared with water-free metal sulfur-containing compounds, such as sodium sulfide, and those prepared from metal hydroxides, such as sodium hydroxide are the following preparations in which equivalent molecular quantities of metalizing reagent were used over a short period of time with dimethylcyclohexyl dithiophosphate.

(a) 1.05 equivalents oi NazS (1.05 moles) 2 dissolved in a minimum of water, heated and stirred with 1.0 mole of dimethylcyclohexyl dithiophosphate at 200 F. rising to 300 F. in 3 hours. Product filtered through paper and tested.

(b) 1.05 moles NaOH dissolved in a minimum of water, heated and stirred with 1.0 mole of dimethylcyclohexyl dithiophosphate diluted with two parts by weight of light neutral oil as diluent (c) 'The same as (b) above but using 1.05 equivalent of NazS (1.05 moles) 2 for the reaction.

Titration of free acidity in the product Mg. KOH/g Original Sample -di-ester acid 135. 4 a. N828 straight 46.0 b. NaOlI, diluted 50/50 as. o c. N818, diluted 50/50 57.0

Thermal test at 325 F. for 16 hours [l per cent additive blend in 170 pale oil.]

Slud 6 Optical Den- Ppt sity Increase acld ester 1 100 565 a. NBzS acid ester straight..- 0 1, 215 b. NaOH acid ester diluted. 1. 745 c. NazS acid ester diluted.-. 10 855 d BaS acid ester diluted 60 745 c. BaO acid ester diluted 60 820 I Taking the acid-ester sludge value as (man).

The un-neutralized acid dithiophosphate produced a heavy sludge with still a light colored residual oil. The NaOI-l product darkened most and produced a heavy sludge, while both of the metal sulfide product gave less color depreciation and remarkably less sludge formation.

Further tests with barium sulfide and barium oxide show that the barium sulfide product has a lower acid value, and the blend in oil shows less color depreciation on thermal treatment than the corresponding barium oxide product.

The above description has emphasized the preparation of metal derivatives of phosphorus sulfide-treated organic compositions in which the combined metal is an appreciable portion of the total organic composition, such as would be from 200 per cent to 1,000 per cent or more of the value shown by the titratable acidity of the phosphorus sulfide-organo-product as obtained in the phosphorus sulfide reaction. In a product of this type I have particularly pointed out the means for producing a high sulfur metal derivative havin excess alkalinity such as has not been heretofore produced but which is now shown as readily producible from metalizing and sulfurizing agents such as the organic or inorganic metal sulfides, polysulfides, hydrosulfides, and the like, under specific conditions of reaction. a

The statement has been made above that the compounds of high sulfur content have not been prepared by the actionof a mixed reagent comprising elemental sulfur and phosphorus sulfide, either together or in consecutive or independent reactions. This does not mean, however, that organo-phosphc-rus and sulfur-containing compositions may not be prepared by such mixed reagents. In fact, a compound prepared by the action of elemental sulfur and phosphorus sulfide in some cases has distinctive properties. The sulfurized organic compositions. such as sulfurized wax olefins, are recognized as having effective metal deactivating and anti-sludging properties. When these are used in combination with a phosphorus sulfide-treated product or a metal derivative of a phosphorus sulfidetreated product, the combined effect is in many cases superior to that which one might reasonably expect from either composition alone. For example, the organo-sulfur compound seems to have particular stabilizing effects upon the phosphorus sulfide addend, such that the phosphorus sulfide composition or blend containing the phosphorus sulfide-treated hydrocarbon appears to have improved storage stability and improved thermal stability. Certain other sulfur-containing organic composition have been found to be particularly synergistic in their action with phosphorus sulfide organo compounds; for example, certain higher molecular weight a iphatic sulfides and disulfides and certain aromatic or alkylated aromatic sulfides and disulfides have been found to have particular activity in this regard. Certain metal derivatives of sulfur-containing compounds, such as the metal salt of phenolic sulfides or alkylated phenolic sulfides and disulfides, have also been found to be particularly effective, especially where the metal salt of such product contributes alkaline reserve to the composition. Such alkaline reserve appears to have particular benefit in stabilizing the otherwise slightly acidic phosphorus sulfide-treated material. A combination of these additives then appears to have unusual stability and thermal dissociation resistance, such that sludging and consequent acid formation in the composition are markedly reduced.

Instead of preparing the phosphorus and sulfur containing intermediate by the reaction of a phosphorus sulfide with an organic compound, as per Example I above, an intermediate product of unusually high sulfur concentration may be prepared by the use of a mixed reagent, i. e. by the simultaneous treatment of an organic compound with elemental sulfur and a phosphorus and sulfur containing reagent. An example of such is given in the following example:

treated with one molal part of elemental sulfur and A molal part of phosphorus pentasulfide under gradually rising temperature conditions to 350 F. and then' held at 350 F. for approximately one hour under an inert gas atmosphere, :1. limpid oily product, dark in color, is obtained which has high oil solubility and particularly desirable additive properties. On a theoretrical basis, this compound should contain 18 per cent of sulfur at the maximum. Upon analysis of the filtered clear reaction product, a value of 16.3 per cent sulfur has been found by gravimetrlc methods which indicates that the product is essentially the sulfur and phosphorus sulfide combined reaction product in which 91 per cent of the theoretical sulfur has been effectively entered into the organo composition.

Example VII To the quantities of PSO-21 diluent and antifrothing agent as in Example II, heated to 200-230 F. four molal quantities of potassium ethyl xanthate are added; the temperature is then raised to 300 F. and held in continuous agitation for one-half to one and one-half hours. For a more rapid reaction the temperature may be raised to 375 F. and held to three-quarters of an hour, under an inert gas atmosphere. The product is centrifuged or filtered.

In similar manner, sodium thiocarbonate is applied.

A particularly interesting and desirable additive has been prepared by the method outlined above in which both a sulfurized olefinic structure and a phosphorus-sulfurized ester type of structure is present. Such a compound has but one olefin bond for sulfurization and, accordingly, is not readily polymerized. Among the fatty acid esters, for example, the methyl or phenyl esters of ricinoleic acid, such a hydroxy-olefin ester structure is available. The fatty acid esters themselves contribute very desirable oiliness properties to a lubricant composition containing them. Further, the sulfurized esters have long been recognized to have high antisludging and anticorrosion properties; however, in the composition here particularly disclosed, a mixture of sulfur and phosphorus pentasulfide may be used to effect the production of a new composition having particularly interesting properties in that a thiophosphoric acid ester type structure is at hand upon which metal derivative compositions may be based, and a sulfurized or phosphorus sulfurized olefin structure is also at hand having the outstanding characteristics above described.

It is evident, that a compound of this type in which sulfur and phosphorus sulfide are combined in one molecule has certain particularly desirable properties for lubricants in which high antisludging, anticorrosion, and metal deactivating functions are required. The additives prepared from such a product have, in addition to the properties of the metal derivatives hereinabove disclosed, the advantages of oiliness, loadcarrying capacity, excellent chemical stability, and outstanding protection to metals exposed to rusting conditions in water-oil systems or oily systems exposed to corrosive water vapor.

A further and perhaps more important and pronounced cooperative effect is the extent to which the combination of addition agents or the union of several functional addition agents in one molecule act to decrease the tendency of refined mineral lubricating oils containing them to be corrosive to metal surfaces, especially those composed of sensitive bearing metals such as cop- 7;, per-lead and cadmium-silver. These additive 31 compositions have an additional advantage of being relatively insensitive to copper, such that the copper bearings are not blackened undesirably as is the case with most sulfurized organic compositions alone.

In certain instances, other addition agents act in a co-operative manner to produce unusual and desirable results. For example, certain halogenbearing acid esters have been employed, such as methyl dichlorstearate, chloro-phenyl palmitate, and the like, which act to produce a highly eflective anticorrosion agent having particular oiliness characteristics which apparently contribute to the additives eifectiveness unexpectedly.

While the above description is of a phosphorus and sulfur containing metal derivative of an organic compound, preferred methods of making the same, and of the use of such compounds as or in lubricant oil, my invention is not limited to such uses since the products of the type here disclosed may be used in other petroleum products such as white oils, greases, waxes. cutting oils, extreme-pressure lubricants, and the like to increase the resistance of such products to oxidation, corrosion, sludging, and to act as metal deactivators to deactivate catalytic metals with which the above products may come in contact.

It is to be understood that the examples given are by way of illustration only and not by way of limitation and that the theories advanced with regard to the action of the phosphorus sulfurized olefins and generally of the metal derivatives of phosphorus sulfurized organic compounds having a high sulfur content are the basis of my conception of these products and their action. I do not wish to be bound by the theory but base my claims upon the improved results which are obtained with these compounds.

The metal derivatives of the present invention may be prepared with various ratios of combined metal and from various metal reactants either as elements or as compounds. I have found, generally, that high thermal stability and outstanding antioxidant, antisludging and anticorrosion characteristics in addition to detergency are brought about by the introduction of an appreciable quantity of combined metal at least of the order of one equivalent of metal per mole of phosphorus-sulfide reaction product, particularly where this is eifected in a manner such that the organic sulfur content is not appreciably reduced and is preferably maintained at the original level, or may actually be augmented.

The metal derivatives of the phosphorus-sulfur-metal products herein disclosed are particularly difierent from those heretofore described in that the metal derivative comprises an appreciable quotient of the total composition, in fact such a quantity of combined metal as to be some multiple function of the original available acidity of the phosphorus sulfide hydrocarbon. These metal derivatives are further characterized by the high sulfur content maintained therein, which high sulfur content has been maintained or augmented by the action of a metal-derivative-forming compound containing a sulfur atom or radical in combination, such compounds being the organic or inorganic metal sulfides, hydrosulfides, disulfides, polysulfides, thiocyanates, mercaptides, sulfonates, thiophenolates, thiocarbonates, xanthates, xanthogenates, and the like. The metal compounds having an efllcacious reaction in this connection are particularly the alkali metals, alkaline earth metals, and other active sulfide-forming metals.

The high sulfur-containing metal derivatives of the phosphorus sulnde reaction products here disclosed have outstandingly superior properties as lubricant additives. In effecting an equivalent inhibition of oxidation, corrosion, sludging, and the like, they are roughly four times as effective as the simple sulfurized olefin and more than twice as effective as the related phosphorus sulfide-olefin products. As little as .01 of 1 per cent of the metal-containing high sulfur compounds of the present invention is effective in appreciably increasin the resistance of the oil containing such additives to oxidation, corrosion, sludging, and the like. Higher concentrations of the additives are eifectively used. As much as 20 per cent or more of the additives may efilcaciously be used under certaincircumstances, producing beneficial results in the lubricant compositions thus prepared. For duty in automotive oils of the typical crankcase oil type, the com ositions herein described are effective in very minute concentrations or in larger concentrations, but are particularly useful in concentrations ranging from .5 of 1. per cent to approximately 4 per cent. In lubricants of the heavy duty or Diesel type where detergency is a requirement as well as oxidation stability, anticorrosion, and antisludging properties, concentrations of the preferred metal-containing phosphorus sulfide compositions in the range of from 1 per cent to 10 per cent are highly eiilcacious in producing the desired heavy duty characteristics inthe lubricating oil composition.

Although the addition agents contemplated hereby have a high degree of detergent action, particularly in certain types of oils. when used as the sole addition agent, highly advanta eous results may be obtained by using these addition agents with others, notably other oil-soluble organic metal compounds, which, themselves, effect a higher de ree of detergency when used in hydrocarbon oils. Examples of such organic metal compounds are the oil-soluble salts of:

, Organic acids produced by oxidation of petro- The oil-soluble metallic phenates may also be used, such as those derived from such phenolic compounds as:

Alkyiated phenols such as cetyl phenol and lauryl phenol Esters of salicylic acid such as lauryl salicylate and cetyl salicylate Halogenated alkyl phenols and esters of phenolic acids such as lauryl chlorophenols and lauryl chlorosalicylate 33 Sulphides and polysulphides derived from phenol and alkylated phenols, such as di(tertiary amyl hydroxy-phenyl) sulphides di(tertiary amyl hydroxy-phenyl). disulphides Specific examples of such detergent addition agents are the following:

Calcium naphthenate Cobalt naphthenate Aluminum naphthenate Aluminum chloropherrvl stearate Aluminum cetyl phenate Calcium oleate Calcium dichlor stearate Cobalt dichlor stearate Calcium phenyl stearate Calcium chlorophenyl stearate Calcium cetyl phenate Calcium lauryl phenate Magnesium phenate of lauryl salicylate Calcium laurylchlorophenate Magnesium phenate of lauryl chlorosalicylate Calcium phenate of di(tertiary amyl hydroxyphenyl) sulphide Calcium salt of mono-cetyl phosphate Calcium salt of di-cetyl phosphate Calcium salt of di-lauryl phosphate Aluminum salt ofmono-cetyl phosphate Aluminum salt of di-cetyl phosphate Calcium salt of mahogany acids (petroleum sulphonic acids) Barium salt of mahogany acids Sodium salt of mahogany acids Chromium salt of mahogany acids Cobalt salt of mahogany acids The metal salts of this invention may advantageously be used with detergents comprising combinations of oil-soluble metallic compounds. Examples of such combinations are:

(a) The combination of a metallic phenate with the metallic salt of this invention.

(b) The combination of an oil-soluble metallic alcoholate with an oil-soluble metallic salt of this invention.

(c) The combination of an oil-soluble metallic phenate with an oil-soluble metallic salt of a sulphonic acid and a metallic salt of this invention.

(d) The combination of an oil-soluble metallic alcoholate with an oil-soluble metallic salt of a sulphonic acid and a metallic salt of this invention.

It is also within the contemplation of the invention to provide the addition agents in the form of a homogeneous concentrate in a suitable oil, said oil containing rather high percentages of the addition agents. Such concentrates may be employed for further blending with a blended lubricating oil in the proportion desired for the particular condition of use.

While mineral oil generally is the principal ingredient oi the blended lubricant, it is not essential that it be the only ingredient other than the addition agents, provided only there is no additional ingredient present which is incompatible with the addition agent. It is within the contemplation of this invention to include, if necessary or desirable, such other addition agent or agents as are commonly added to improve certain specific properties of the oil, such as cold test, oiliness, 'anticorrosion, stability to oxidation, detergency, and the like.

When used in conjunction with a blended hydrocarbon oil, it is to be understood that, generally, only such amounts of the additive be inpositions with the above described properties,

mineral lubricating oil is preferred as the additive carrying medium; however it is within the intention of the disclosure to include in the blended oil other components such as vegetable oils, animal oils, synthetic oils, light oil distillates, or aromatic solvents in which these additives may be dissolved or dispersed with substantial permanence.

The materials prepared in accordance with the present invention can be employed for a large variety of uses in which wetting, penetrating, de-

tergent, emulsifying and other interface modi-- fying functions are required. Illustrative of some of the many purposes for which these materials can be used are: as antirust agents in automobile radiators, for dispersing pigments and the like in liquid vehicles, as a penetrating agent in leather dressings, as a penetrating and/or emulsifying agent in cosmetics, as a fat splitting agent, and as wetting and/ or emulsifying agents in combination with mineral oils or fatty oils, for slushing oils, soluble oils, cutting oils, textile lubricants, drawing lubricants and many others.

Corrosion in heat-exchange devices, such as, for example, automobile radiators, can be inhibited by adding small amounts, for example, from about 0.5 per cent to about 5 per cent of the products of the present invention to the heat-exchange medium such as water or aqueous mixtures containing freezing point depressants such as ethanol, methanol, glycerol, ethylene glycol, etc. The heat exchange medium may also contain an emulsifying agent and as a salt of sulfonic acids obtained in the sulfuric acid treatment of mineral oils.

Compositions useful as textile lubricants may comprise from about 50 per cent to about per cent of a highly refined low viscosity mineral oil, having a viscosity of about 60-90 seconds Saybolt Universal at F. from about 1 per cent to about 20 per cent of fatty acid, such as oleic acid, from about 0.5 per cent to about 40 per cent of an alkali metal soap of the sulfonic acids derived by the treatment of mineral oils with sulfuric acid and from about 0.5 per cent to about 10 per cent of a phosphorus sulfide reaction product of the present invention.

Soluble oils suitable for use in metal working operations may contain from about 60 per cent to about 35 per cent lubricating oil, 0.5 per cent to about 10 per cent of a reaction product of the present invention, from about 10 per cent to about 30 per cent of a petroleum sulfonic acid soap. Other constituents such as water, alcohol, oleic acid, bacteria controlling agents, etc, can be included.

Compositions, otherwise, known as slushing compounds, adapted to be applied to metal surfaces to prevent or inhibit rusting and/or corrosion, containing from about 0.5 per cent to about 10 per cent of a product of the present invention, and mineral oil are very effective. These slushing compounds may contain in addition to petrolatum, a soap or preferentially oil-soluble petroq leum sulfonic acid wax, and/or other derived ingredients.

It will be understood that as certain features and subcombinations are of utility they may be employed without reference to other features and subcombinations. This is contemplated by and is within the scope of my claims. It is further obvious that various changes may be made in the field within the scope of my claims without departing from the spirit of the invention. It is, therefore, to be understood that this invention is not to be limited to the specific field shown and described.

Other modes of applying the principle of the invention may be employed, change being made as regards the details described, provided the features stated in any of the following claims or the equivalent of such be employed.

I therefore particularly point out and distinctly claim as my invention:

1. The metal and phosphorus and high sulphur product produced by heating a phosphorus and sulphur-containing organic compound of molecular weight at least 150 with a combining amount of a metal salt of carbon-sulphur acid, of the class consisting of thiocarbonates and xanthates.

2. The metal and phosphorus and high sulphur product produced by heating a phosphorus and sulphur-containing organic compound of molecular weight at least 150 with a combining amount of a metal salt of carbon-sulphur acid, of the class consisting of thiocarbonates and xanthates.

3. The metal and phosphorus and high sulphur product produced by heating a phosphorus and sulphur-containing hydrocarbon wax having an unsaturated content with a metal salt of carbon-sulphur acid, of the class consisting of thiocarbonates and xanthates.

4. The metal and phosphorus and high sulphur product produced by heating a phosphorus and sulphur-containing organic compound of molecular weight at least 150 with a combining amount of an alkali metal thiocarbonate.

5. The metal and phosphorus and high sulphur product produced by heating a phosphorus and sulphur-containing olefinic compound of molecular weight at least 150 with a combining amount of an alkali metal thiocarbonate.

6. The metal and phosphorus and high sulphur product produced by heating a phosphorus and sulphur-containing hydrocarbon wax with a combining amount of an alkali metal thiocarbonate.

'7. The metal and phosphorus and high sulphur product produced by heating a phosphorus and sulphur-containing organic compound of molecular weight at least 150 with a combining amount of potassium ethyl xanthate.

8. The metal and phosphorus and high sulphur product produced by heating a phosphorus and sulphur-containing olefinic compound of molecular weight at least 150 with a combining amount of potassium ethyl xanthate.

9. The metal and phosphorus and high sulphur product produced by heating a phosphorus and sulphur-containing hydrocarbon wax with a combining amount of potassium ethyl xanthate.

10. The method of producing a metal and phosphorus and high sulphur product, which comprises heating a phosphorus and sulphur-containing organic compound of molecular weight,

' at least 150 with a combining amount of a metal salt of carbon-sulphur acid, of the class consisting of thiocarbonates and xanthates.

11. The method of producing a. metal and phosphorus and high sulphur product, which comprises heating a phosphorus and sulphur-containing olefinic compound of molecular weight at least with a combining amount of a metal salt of carbon-sulphur acid, of the class consisting of thiocarbonates and xanthates.

12. The method of producing a metal and phosphorus and high sulphur product, which comprises heating a phosphorus and sulphur-containing hydrocarbon wax with a combining amount of a metal salt of carbon-sulphur acid, of the class consisting of thiocarbonates and xanthates.

13. The method of producing a metal and phosphorus and high sulphur product, which comprises heating a phosphorus and sulphur-containing organic compound of molecular weight at least 150 with a combining amount of an alkali metal thiocarbonate.

14. The method of producing a metal and phosphorus and high sulphur product, which comprises heating a phosphorus and sulphur-containing oleflnic compound of molecular. weight at least 150 with a combining amount of an alkali metal thiocarbonate.

15. The method of producing a metal and phosphorus and high sulphur product, which comprises heating a phosphorus and sulphur-containing hydrocarbon wax with a combining amount of an alkali metal thiocarbonate.

16. The method of producing a metal and phosphorus and high sulphur product, which comprises heating a phosphorus and sulphur-containing organic compound of molecular weight at least 150 with a combining amount of potassium ethyl xanthate.

17. The method of producing a metal and phosphorus and high sulphur product, which com- JOSEPH M. HERSH.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,772,386 Derby Aug. 5, 1930 2,034,665 Ott Mar. 17, 1936 2,063 629 Salzberg et al Dec. 8, 1936 2,316,091 White Apr. 6, 1943 2,342,431 Smith Feb. 22, 1944 2,343,213 Ashley Feb. 29, 1944 2,344,395 Cook et al. Mar. 14, 1944 2,347,592 Cook et al. Apr. 25, 1944 2,348,080 Lincoln May 2, 1944 2,362,624 Gaynor et al. Nov. 14, 1944 2,372,358 Cook et al. Mar. 27, 1945 2,377,955 Mixon June 12, 1945 2,382,775 Cook et al. Aug. 14, 1945 

1. THE METAL AND PHOSPHORUS AND HIGH SULPHUR PRODUCT PRODUCED BY HEATING A PHOSPHOROUS AND SULPHUR-CONTAINING ORGANIC COMPOUND OF MOLECULAR WEIGHT AT LEAST 150 WITH A COMBINING AMOUNT OF A METAL SALT OF CARBON-SULPHUR ACID, OF THE CLASS CONSISTING OF THIOCARBONATES AND XANTHATES. 